Azo-dyestuffs



Patented Sept. 8, 1936 UNITED STATES AZO-DYESTUFFS Friedrich Felix and Wilhelm Huber, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application March 21, 1935, Serial No. 12,299. In Switzerland March 24, 1934 9 Claims. (Cl. 260-92) 7 This invention relates to the manufacture of dyestuffs by coupling a diazotized aromatic amine of the general formula (R representing hydrogen, alkyl, aralkyl or aryl) e. g., an acidylamino-group, such as an acetylaminoor benzoylamino-group, with a coupling component of the general formula in which A stands for a nucleus of the naphthalene series which carries a sulfo-group, and R1 and R2 each stand for hydrogen, alkyl, aryl or aralkyl radicals, the conditions of coupling being chosen in such a manner that the 7 N =group is the group which causes coupling.

The term alkyl radicals comprises not only the radicals of hydrocarbons, such as methyl, ethyl, propyl or butyl radicals, and the like, but also, as. used in the scientific literature, cf. "Anthracene and Anthraquinone by E. de Barry Barnett, London 1921, page 207, and in the patent literature of. British Patent 26,336/ 1910 Claim 1, substituted alkyl radicals, for example, alkyl radicals substituted by halogen, such as, for example, chlorobromoor iodo-ethyl radicals, alkyl radicals substituted by OH-groups, such as hydroxyethyl-, hydroxypropyb, hydroxybutylor dihydroxy ropylene radicals, further the ethers and esters thereof, such as methoxyethylor acetoxyethylor ethylsulfuric acid radicals, further also alkylcarboxylic acid radicals and their derivatives, such as propionic acid radicals orpropionic ester radicals or propionic acid amide radicals, or the radicals of ethylnitrile or ethylsulfocyanide. The arylor aralkyl-radicals R1 and R2 may also be substituted in the arcmatic nucleus.

As products of the general formula there may be named, for instance, 1-amino-4- nitrobenzene-2-methyl- (or 2-ethy1 or 2-benzylor 2-hydroxyethyl or 2-hydroxybenzylor 2- carboxymethylor carboxymethylester-methyl)- sulfone, the corresponding 1-amino-4-nitro-5- chlorobenzene-2-alkylsulfones, the corresponding l-amino-4-nitro-6-chlorobenzene-2-alkylsulfone, the corresponding sulfones in which the chlorine is exchanged for bromine or iodine, and l-amino- 4, 6-dinitrobenzene-2-methysulfone, further the 1 amino-4-acetylaminophenyl 2 methylsulfone, the 1-amino-4-acetylaminophenyl-2-ethylsulfone, the 1 -amino chloro-4-acetylaminophenyl-2- methylsulfone, the 1 amino 4 -benzoylaminophenyl 2 methylsulfone, the 1 amino 4 (4'- methoxy) -oenzoylaminophenyl- 2 -methylsulfone, the 1-amino-4- (4'-chloro) -benzoylaminophenyl- 2-methylsulfone, the 1-amino-4-benzoylaminophenyl-2-ethylsulfone, the 1-amino-4-benzoylaminophenyl-2-benzylsulfone, the 1-amino-4- phenoxyacetylaminophenyl- 2 -methylsulfone, the 1 amino 4 (4 '-ethoxy) -phenoxyacetylaminophenyl-Z-methylsulfone, 1-amino-4- (2'-methyl) phenoxyacetylaminophenyl- 2 -ethylsulfone, the l-amino- 4 -phenylacetylaminophenyl 2 methyl sulfone, the 1-amino-4-dimethylaminophenyl-2- ethylsulfone, the l-amino-4-diethylaminophenyl- Z-ethylsulfone, and the like.

As coupling components'oi the general formula also explainedabove, there are suitable any sulfonated aminonaphthalene compounds capable of coupling, such as the true sulfonic acids of the following compounds: ccand fi-naphthylamine, 1-N-methoxyethylaminonaphthalene of the formula 2 N methoxyethylaminonaphthalene, 1 N

hydroxyethylaminonaphthalene, Z-N-hydroxyethylaminonaphthalene, further aminonaphthols such as, for example, l-amino-S-hydroxynaphthalene, l-amino-fi-hydroxynaphthalene, l-amino-7-hydroxynaphthalene, 1-amino-8-hydroxynaphthalene, 2amino-3-hydroxynaphthalene, -2-

amino-4-hydroxynaphthalene, 2-amino -.5 hydroxynaphthalene, 2-amino-6-hydroxynaphtha contains no phenolic OH-group in the aromatic nucleus A of the naphthalene series, the expression fcoupling conditions in which the amino group causes coupling means-the coupling of the component in neutral or acid. medium usual for aromatic amines. However, if the aromatic nucleus A contains one .or more phenolic OH-groups, coupling should be carried out in acid medium. But, as is well known, the selection of the coupling conditions in sucha manner that the amino group of a coupling component is the group which causes coupling does not present a problem to the expert, but a knownmeasure.

. V The dyestufisthus'produced' can be converted into other valuable products by treating-them withsuitablereducing agents so that the nitrogroup of the diam-component is reduced, and, if desired either acylating or alkylating the new amino-group .bymaansof the usual agents, or

converting the reduced bodyinto other dyestuffs by diazotizing the amino-group and coupling with suitable coupling-components.

The'new dyestufis'correspond therefore to the general formula in which X stands for a nitrogenous group which islinked with its nitrogen. atom to the aromatic nucleus, such, as an NOz-group, an NHz-group, an

alkyl .N\ =group alkyl I]I--(l}J-Ri= 1 P H o (R1 representing hydrogen, alkyl, aralkyl or aryl) i. e. an acetylamino or benzoylamino-group, a phenylacetylaminoor phenoxyacetylaminogroup, Y stands for a sulfone radical of the general formula SO2--CH2R (R representing H, alkyl or aryl), A for a sulfonated aromatic nucleus of the naphthalene series, and B for an amino-group wherein R stands for H, alkyl or aralkyl, which amino-group stands in 2- or 4-position to the N=N-group.

The dyestuffs thus obtained are red to black powders, which are excellently suitable for dyeing textiles of various kinds, for example wool and silk, and are also suitable for dyeing lacquers, varnishes and plastic masses.

They are dark powders dissolving in water with addition of alkalies to orange, to red, to violet and blue solutions and dyeing wool from an acid bath similar tints of good fastness properties. Among these dyestufis those are particularly valuable which derive from the 2-aniino-8-hydroxynaphthalene-6-sulfonic acid, and among this smaller group those dyestuffs in which the group X stands for an N -acidyl-group, particularly an N-acetylamino-group or an N-benzoylamino-group. These dyestuffs correspond to the general formula in which R stands for hydrogen, alkyl or phenyl. They are dark powders, dissolving in water with addition of alkali'e's to red to Bordeaux red solutions, and dyeing wool similar tints of very good fastness, particularly excellent fastness to light, which are very level.

The following examples illustrate the invention, the parts being by weight-- Ezrample 1 ;QN=N

-The substitution of the 2-amino-5-nitro-phenylbenzylsulfone by the corresponding methyl or ethylsulfone leads to violet dyestuffs. By cautious reduction and acylation of the NHz-group thus produced there are obtained products which may be identical with those of the following example.

' Example 2 242 parts of 2-amino-5-acetylamino phenyl ethylsulfone are converted into the diazo-compound by addition of hydrochloric acid and 69 parts of sodium nitrite. Into this diazo-solution there is introduced a neutral solution of 239 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid and the reaction is accelerated by addition of sodium acetate. The dyestuif is filtered and washed. It is a dark red powder, which dyes wool in an acid bath fast bluish red tints. The dyestuif corresponds with the'formula Similar dyestuffs are obtained by using analogous sulfones as diam-components, for example 2-amino-5-acetylamino-phenylmethylsulfone or 2 amino 5 acetylaminophenylbenzylsulfone. Further, instead of the N-acetyl-compounds, the N-benzoyl-odmpounds may be used or the chloroaectyl-compounds or the like. In this casered to violet dyestuffs are obtained which have good dyeing properties.

In the following table there are listed some other dyestuffs obtainable in accordance with this invention:

- Color of the Diem-component gg gggg 501312;); in sgg on 1 2-amino-5-nitro- 2-amino-8-hy- Blue-violet Red-blue phenyl-ethyldroxy-naphsulfone thalene-fi-sulionic acid (acid coupled) 2 2-an1iuo-5-nitr0- do do Do.

phenyl-rnethylsulfone 3 2-a1nino'5-acetyl- 2-amln0naph- Red-orange Redamino-phonylthaleue-G-sulorange methylsulfone fcnic acid 4 do 2-emino-8-hy- Rod Bluish-red dr oxy-naphthalene-(S-sulionic acid (acid coupled) 5 2-a1nino-5-acetyl- 2-aminonaphtha- Scarlet Scarlet amino-phenyllene-fi-sulionic benzylsulfone ac 6 2-u1niuo-5-ben- 2-amino-8-hy- Bordeauxm- Bordeaux zoylaruinodreary-naphphenylmethylthalene-G-sulsulfone ionic acid (acid coupled) 7 2-amino-5-nitrc- 2-phenylamino- Grecn-blue Green-blue phenyl-meth- Shydroxyylsulfoue naphthalene- (i-sulfcnic acid (acid 00 uplcd) 8 2-amino-5-nitrol-amiuo-S-hydo Do.

phenyl-methdroxy-naphylsulfone thalene-7-sulionic acid (acid coupled) Example 3 2.5 parts of the dyestuff obtained as described in Example 2 are boiled with 1000 parts of water. A dye-bath is prepared with 2500 parts of water at 50-60 C. to which there are added the dissolved dyestuff and 500 parts of water rinsings. To the dye-bath comprising 4000 parts of liquor there are added 10 parts of crystallized sodium sulfate; 100 parts of wool are entered at 50-60 C. and 40 parts of sulfuric acid of 10 per cent. strength are added. The whole is warmed gradually to 85-90 C. and dyeing is continued for 1 hour at this temperature. The usual finishing operations follow, whereby there is obtained a very pure bluish-red dyeingof excellent properties of fastness.

What we claim'isf 1 1. The 'azo-dyestufis of the'general formula in which X stands for a nitrogenous group selected from the group consisting of the nitro group, acyl-amino groups and dialkyl-amino groups and which is linked with its nitrogen atom to the aromatic nucleus, Y stands for a sulfone radical of the general formula SO2-'-CH2R1,'R1 stand-' ing for a; member. of the group consistingof hydrogen, alkyl and phenyl, in which formula further the naphthalene nucleus is sulfonated and does not contain more than one phenolic OH-group, one Z stands for an aminogroup and the other Z for a hydrogen atom, the naphthalene nucleus carrying no other amino-groups than the aminogroup Z, which products are dark powders soluble in pyridine to red, violet, blue and green solutions and dyeing lacquers and the fiber red to blue and green tints.

2. The azo-dyestuiis of the general formula in which X stands for a nitrogenous group selected from the group consisting of the nitro group, acyl-amino groups and dialkyl-amino groups and which is linked with its nitrogen atom to the aromatic nucleus, Y stands for a sulfone radical of the general formula SO2CH2-R1, R1 standing for a member of the group-consisting of hydrogen, alkyl and phenyl, and one Z for an NH:- group and the other Z for a hydrogen atom, which products are dark powders soluble in water with addition of alkalies to red to violet, blue and green-blue solutions, and dyeing wool from an acid bath fast red to violet to blue and greenblue tints.

3. The azo-dyestuifs of the general formula soul in which Y stands for a sulfone radical of the general formula SO2CH2R1, R1 standing for a member of the group consisting of hydrogen, a1- kyl and phenyl, which products are dark powders soluble in water on addition of alkalies to red to Bordeaux-red solutions and dyeing the wool in an acid bath blue-red to Bordeaux-red tints.

4. The azo-dyestuffs of the general formula in which the alkyl radical is not substituted and doessnot consist of more than two carbon atoms, which products are dark powders soluble in water on addition of alkalies to red to bluish-red solutions and dyeing wool in an acid bath fast bluishred tints.

5. The azo-dyestuifs of the general formula I] I l in which the alkyl radical is not substituted and does not consist of more than two carbon atoms, and in which R stands for an aromatic nucleus of the benzene series which products are dark powders soluble in water on addition of alkalies to Bordeaux-red solutions, and dyeing'wool from a acid bath fast Bordeaux-red tints. 6. The azo-dyestuffs of the general formula I O T! N=N 40 0 B Q SOrCH; HO

. SOaH which product is a dark powder soluble in water on addition of alkalies to a Bordeaux-red solution, and dyeing wool from an acid bath fast Bordeaux-red tints.

'8. 'I'he'azo-dyestuff of the formula which product is a dark powder soluble in water on addition of alkalies to a blue solution, and

dyeing wool from an acid bath fast blue tints. 9. The azo-dyestufis of the general formula S OPCH R Y in which R stands for a member of the group consisting of hydrogen, alkyl and aryl and Y for an amino-group, which products are dark powders soluble in pyridine to violet, blue and green solutions and dyeing the fiber violet to blue and green tints.

FRIEDRICH FELDI.

WILHELM HUBER. 

